Glyceride compositions containing betaine derivatives



Patented Jan. 2, 1951 GLYCERIDE COMPOSITIONS CONTAINENG RETAIN E DERIVATIVES Sol Shappiric, Washington, D. C.

No Drawing. Original application .iune 26, 194%,

Serial No. 542,255. Divided and this application October 8, 1947, Serial No. 778,725

16 Claims.

This invention relates to glyceride containing compositions, to additions therefor, and to methods of making such additions and compositions and to their utilization, particularly to additions based on betaines and their modifications.

Among the objects of the present invention is the production of glyceride compositions containing betaine derivatives which have a beneficiating effect on said glycerides.

Other objects include the production of novel betaine derivatives for such utilization.

Still further objects and advantages will appear from the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of illustration and explanation only, and not by way of limitations, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

In accordance with the present invention it has been found that compounds such as betaines and other compounds disclosed in application Serial No. 154,937, filed July 21, 1937, entitled Antioxidants, now Patent No. 2,217,711, granted October 15, 1940 and compositions and materials derived from betaines disclosed in application Serial No. 361,151, filed October 14, 1940, entitled Compositions Containin Antioxidants, now Patent No. 2,352,229, granted June 27, 1942; may be treated and new derivatives produced for utilization which greatly enhance the beneficiating properties such as antioxidant characteristics of the materials in glyceride compositions and for other utilities. The present application is a continuation-in-part of the stated applications identified immediately above. The present application is a division of application Serial No. 542,255, filed June 26, 1944, now Patent No. 2,430,031.

In explanation of the present invention it is desirable to point out the material disclosed in the prior specifications above identified. In Serial No. 154,937 there are described and claimed particularly antioxidants which may be either chemical entities or synthesized chemical entities built up synthetically, either from the individual ccmponents ultimately reacted to give the complex organic derivatives of desired antioxidative value, or they may be formed by synthetically utilizing naturally occurring materials as a basis for one of the components, the synthetic antioxidants being produced directly in situ by synthesis from such naturally occurring materials.

The betaines may be directly employed as antioxidants. Betaine itself is available as a byproduct from beet sugar manufacture, betaine all 2 being found extensively in sugar beets, and also in other vegetable products, and in animal products, such as shell fish. It may be readily produced synthetically by oxidizing choline, and in other Ways. Its ready availability in the residues from beet sugar manufacture, such as in the so-called melasse gives a ready source for its derivation. Other natural occurring betaines,'

such as trigonelline, obtained from the seeds of fenugreek, may similarly be employed, and the melasse or other sugar beet residues containing the betaine or the seeds of ienugreek may be employed as antioxidants utilizing the desired materials in powdered condition, or in suspension, in contact with the substances to be protected against oxidation, particularly as further pointed out below.

Instead of utilizing the betaines represented by betaine directly as an antioxidant, the betaines may be utilized for the production of alkylaminoalkyl-phosphoric acid esters analogous to those obtained from choline. The resulting products are alkylamino-alkyl-phosphoric acid esters that can be utilized for antioxidant purposes. The melasse may be treated directly with the distearyl-phosphoric acid ester for example, 'or

other phosphoric acid ester of a diglyceride to Since the produce corresponding antioxidants. betaines are acid bodies, they may be utilized for production of esters by reaction with alcohols, particularly the unsaturated alcohols, and also the amino alcohols, as well as the lipoid alcohols, like phytosterol, for the production of esters utilizable as antioxidants.

The antioxidants including the betaines and the alkylamino-alkyl-phosphoric acid esters, may be employed for the protection of a wide variety of materials against oxidation, such as by the addition of a fraction of a percent to oils or fatsto protect the latter against oxidation, or they may be dusted on food products to protect the latter against development of rancidity, or undesirable change in the oils or fats contained in such edible products. Or packaging materials carrying the stated antioxidant may be produced, such as paper carrying a sizing coating employed as a Wrapper for products to be protected against development of rancidity.

In application Serial No. 351,151 identified above, there is particularl described and claimed the conversion of betaines and other derivatives disclosed in the earlier application, into fatty acid derivatives of the betaines to increase their coinpatibility for or solubility in glyceridcs, etc. Any

- of the betaines described above such as betaine it fat oils, etc, as well as in connection with,hyd ro-,,

carbon oils.

The fatty acids that can be employed in pro;

ducing the desired derivatives include more particularly the higher fatty acids, specifically. the fatty acids occurring in glyceride oils themselves,-

used either as such or in complex mixtures of.

two or more of such higher fatty acids, particuiarly the complexes which are produced from the fats or oils themselves by saponification and liberation of the acid. As exemplary of the glyceride oils which may be employed as a source ofv the fatty acids utilized in producing the betaine derivativ @m g 1 c p il ncc thfihat nvention; there are mentioned almond oil yielding oleic, palmitic linoleic, etc. acids, butterfatyieldir g butyric, caproic, capric, palmitic, stearic, oleic, etc. acids; cacao butter giving palmitic, oleic, stearic, myristi etc, acids; castor oil giving r ic-, inoleic, stearic, oleic acids, etc.; cocoanut oil yielding caproic, capryiic, capric, lauric, etc. acidsicodliver oil givingoleic, myristic, paimitic, stear etc. acids; cottonseedoil giving oleic, stearic, palmitia linoleic, etc.acids; hemp oil giving isol'nglenic, oleic, etc. acids; lardgivingstearic, p a l mitic, ol'eic, lineleic, etc. acids; linseed oil yielding linoleic, linolenic, oleic, palmitic, myris: tic, etc.'acids; maizeoilgiving arachidic, stearic, palmitic, oleic, etc, acids; menhaden oil giving palmitic, myris tic, oleic, stearic, and other un saturated acids, etc.; mustard oil yielding erucic, ara hidic, stearic, oleic, etc. acids; neats-foot oil giv ngpalmitic, Stearic, oleic, etc. acids; olive oil yielding linoleic, oleic, arachidic, etc. acids; palm Qilj iviue mitic. a l a c. d tre nut .1. ie i aaresh it. i e c hyposoeic, p lmitic, etc. acids poppy. oii giving linoleic, isolinolenic, pa l mitic, stearic, etc. acidsyrape oil yielding erucic, arachidic, stearic acids, etc. sperm oilgiving oleic, palmitic, etc. acids; tallow yielding stearic, palmitic, oleic acids; 7 whale oil yielding linolei c, isolinolenic, etc, acids. The com-.

plexacid mixtures obtained from any of the oils may be utilized, or the individual acids or desired mixtures thereof may be employed in producin thebetaine derivatives.

tures thereof may be utilizedwitha betainebut mixed acid derivatives may be employedinclud: ing the fatty acid component particularly higher fatty acid component as set forth above, together with either an inorganic acid or an organic acid Complexes may thus be produced in whichvderivatives of the/fatty acids and of other organic acidaorinorganic acids are alsopresent, partic ularly for utilization as antioxidants in connection with glyceride or hydrocarbon oils.

Where the betainederivatives are employed in connection with glycerides or otheroils for ediblev purposes, the derivatives of betaine are produced with acids thatare wholesome and available for edible purposes.

Where, however, th ultimate product is e1 n. ployed for non-edible purposes as in connection with hydrocarbon oils employed as lubricants, or. motor fuels, or glyceride oils employed; for coatmg and; other purposes, then acids may be em As there taught, any of the fattyacidsor mix.-.

different from said fatty acid initially employed.

4 ployed in producing the complexes which are not limited to edible acids. Thus linseed oil acids, tung oil acids, etc. may be utilized to produce the betaine derivatives. The same considerations apply to the utilization of inorganic acids or organic acids other than the fatty acids in the proi t on O ixed. ativeaqf hebet in With thefatty acid and inorganic-acids or organic acids other than the fatty acids may be employed in such complexes where they are utilized for edible purposes, such other acids being chosen with re- 7 spectto their availability for use in the human or other animal bodies; whereas different types of acids maybeemployed if the product is not to be used for edible purposes.

As, illustrative of inorganic acids they may be utilizedin producing mixed complexes and derivatives as taught therein, reference is made to phosphoric, sulphuric, nitric, and other inorganic acids, while organic acids-other than the fatty acids hatm y be m loyed in lude. an ofth aliphatic, aromatic and'heterocyclic acids such as benzoic, phthalie, succinic, tartaric, lactic, naphthenic, t a i s.

And' that case particularly emphasized: the utilization of' fatty acid as derivatives of; the betaines as such or -'as mixedfatty acid esters or as mixed derivatives of'betaines with fatty acids and inorganic acids or organic acids other than fatty acids, as antioxidants in the; protection f various types of' oils, fats and similar materials subject to oxidative deterioration.

It-has now beenfound that antioxidants and other materials as set ferth in the prior applications above identified, may-be materiallyincreased in thei r activity as antiexidantsand'inother waysby combination of; such cempo unds with the sugars, including aldosesand ket oses, both monosaccharides, disaccharides; etc. Such sugars-may thus be converted into es ter s;when compounds containing acid groups'such as thebe taines are m l d r i i i i ic el v h i elwmr binations.v The; f ormation of such combinations with betaines will be illustrative,

Any of the sugarssuchfas a hexosemay be, esterifled 'by a betaine by the ;usual"methods of; esterification. Thus approximately 18 parts, of a; e e like xt seareheat iihirom ah.- pvroxim ie y, .11 024 zparts, ij ta ne sale.d; e c i n v sel. nder. Pre surefi a ures. of a p ox mate 1.1 0? n' o s. and h eact on. r d ct outaining he-nex e. ester with 1 the b etaine removed' frpm the vessel n ed. s nantioxi enhie aelr ridesoili i r r. urposes. ssetiofih b ve Qnepr; more of the e a ne esiduea y hee erifiedmto. the,hexose,,molecule. Any of; the other sugars may similarly be treated; Suc est r asu ar i h. arbeteinemar. be utilized. nuan iox dant. n .i. .is. s. t1 9tth, above, or may be furthertreated; in a variety, fw y o ducederivat sthereof-. Th she. comp ex. odu ed;bvre c na asu a ith. e n l s ratcd' bov may. e e il treated with an acid either;organic,'Or inOrganic or acombination of such acids, selected frorn the ac s. set. forth. abo e. op c luce. eycre jt pss o e iv lie r en aacids.suchas afat y. a id 1 e,inorga ic. sicla innas.bhcsphpric cid. ma fiti ized 1 his. e, aest ri r u lhe droxyl rou in t e. zmclec la n o. produce an er. with han .dmxylsroiip at: a i dtoth itr en mine. eteineres duap bot c ubst t tion art keplace Irma. ne essar o 11.eat... hc ugar; .09... punctuate;

betaine at moderate temperatures of from 60 to 70 C., with the acid or. mixture of acidswhile stirring, for periods of from 2 to 3 hours to produce the desired combinations. The resulting compounds may be illustrated by the following formulae.

A mono ester of a sugar with a betaine may be represented by the formula S.CO.Bx, where S stands for the sugar residue, and CO.Bx stands for the betaine residue.

- Thus the ester produced from betaine and dextrose in the example given above is illustrated by the formula.

' CHO. (CHOH) 4CH2O.CO.CH2N (CH3) 30H Where the acid is reacted into one of the remaining hydroxyl groups in the sugar residue of the ester of the sugar with the betaine, the resulting compound may be represented by the formula A.S.CO.Bx, where A stands for the acid radical, S for the sugar residue, and CO.Bx for the betaine residue. Where the acid radical is attached to the 01-1 of the betaine residue and not to the sugar molecule, the formula is S.CO.Bx.A. where the letters have the significance indicated immediately above. And. the compounds where the acid is combined into both the sugar residue and the betaine residue is represented by the formula A.S.CO.Bx.A, where the letters have the significance indicated immediately above.

In producing such derivatives where organic or inorganic or mixtures of such acids are utilized to produce further combinations, it is not necessary to prepare individual compounds in a series of reactions, but the components may be heated together to produce a complex containing mixtures of reaction products of the character de scribed immediately above. Thus, a sugar, a betaine, and an organic or inorganic acid or mixture of acids selected from those set forth above, may be reacted simultaneously under conditions normally employed for esterification purposes. Thus 18 parts of levulose, 12 parts of betaine, and 28 parts of oleic acid (the parts being by weight) are heated together in a sealed reaction vessel under pressure for 8 hours at a temperature of approximately 140 C., and the resulting reaction complex containing various combinations as set forth above may be utilized as such as an antioxidant in accordance with the present invention.

The presence of aldose and ketose groups in these combinations enables the sugar-betaine reaction products to be utilized for the preparation of still further complexes, as for example, in their conversion into hydrazones and osazones by reaction with aldehydes and ketones, aliphatic, aromatic and heterocycic. The preparation of such derivatives will be illustrated below in connection with related compounds. The usual methods for forming such hydrazones and osazones may be employed.

Instead of converting the betaine into a combination directly with the sugar, the betaine may first be converted into an amide or hydrazide, such amides or hydrazides of the betains being known produced for example, by the treatment of betaine esters with ammonia or with hydrazine. The amide may be represented by the formula- NH2.CO.BX, where CO.Bx again represents the betaine residue. The hydrazide may be represented by the formula NH2.NH.CO.BX, where again COBx is the betaine residue. Thus the amide of betaine" would have the formula nn cocrrzrr can 30H while the corresponding hydrazide of betaine per set would be NH2NH.CO.CH2N(CH3)3OH. The amides and hydrazides of the betaines are valuable per se. as antioxidants and exhibit marked activity as such antioxidants in glyceride oils and. hydrocarbon oils. For the latter, the solubility should be increased by having present sufficient long chains as in the betain residue to give the desired solubility.

The amides and hydrazides of the betaines as set forth above, may be converted into acid salts, esters or soaps by the use of either organic or inorganic acids of the character set forth above. Again various combinations may be produced depending on whether the acid is at.- tached to the hydroxyl group of the betained residue, or whether it is attached to a nitrogen of the amido or hydrazido group. These combinations of the acids with the betaine amides or hydrazides may be produced analogously to the methods set forth in the companion application for the preparation of the fatty acid derivatives of the betaines themselves, by heating the amides or hydrazides with the selected acidat moderate temperatures such as 60 to 70 C. for 2 to 4 hours. Thus betaine amide may be heated with lauric acid using approximately 12 parts of the betaine amide with from 20 to 60 parts of lauric acid depending on the type of derivatives desired. The resulting complex produced under the conditions set forth immediately above includes a complex mixture of derivatives of the character illustrated with the lauric acid bound into the betained amide molecule; and such complexes may be used themselves without segregation of the individual component as antioxidant in connection with glyceride oils for example, as set forth above.

The compounds thus produced may be formulated as follows. Where the acid is bound into the compounds through the hydroxyl of the betaine residue, it is illustrated by the formula NH2.CO.BX.A, where CO.Bx represents the betaine residue and A represents the acid residue. Where the acid is attached t the amino group at the amide end of the molecule, the compound may be formulated as A.NH2.C0.Bx, where the letters have the significance indicated above. And where the acid is bound both through the betaine residue and the amino group of the amido end of the molecule, the compound may be formulated as A.NH2.CO.BX.A, where the letters have the significance indicated above. Thus in the specific example Where lauric acid is used to produce the complex, the A in the formulas given immediately above will be the lauric acid group. A

The betaine hydrazides may be reacted with aldehydes and ketones, aliphatic, aromatic and heterocyclic to give valuable hydrazones or os-'j azones. For example as aldehydes there may be mentioned acetaldehyde, benzaldehyde, furfural, and sugars containing an aldehyde group such as grape sugar; as ketones there may be men-i tioned acetone, benzophenone, sugars containing ketone groups, etc. Such production of hydrazones may be carried out by the usual methods of producing hydrazones, or they maybe pro,- duced in situ in the oils in which they are to be utilized as antioxidants. As an example-of preparing such a hydrazone in situ, the following is iven.

A hydrocarbon distillate containing approxie mately 1% by weight of betaine hydrazide is. agitated with benz aldehyde and glacial acetic a' 'cidusihg 1 pound oi-henzaldehydeto 100 pounds of distillat'e, until reaction iscomplete; usually requiring several hours. The mixture is allowed to settle, the aqueous layer withdrawn and the" hydrocarbon layer washed with dilute alkali until neutral. The hydrazones produced in such 8X-- ample will havethe formula where COLBX. represents. the betaine residue. Similarly aliphatic, carbocyclic, heterocyclic a1-' dehydes and. ketones may be employedin producing' hydrazonesi generally formulated as R.CH;=N.NH.CO.BX, wheree RICH represents the aldehyde residue, and CO.BX represents thebe tainearesidue. Where. a ketone is employed for producing the hydrazone, the resulting hydrazone. will have i the formulation o=n.NHoo.Bx

whereR'representsthe organic group present in the ketone employed.

Thehy drazone formed from benzaldehyde and b'etaine hydrazide in the example given has the particular formula I;f-.benzophenone is used to-produce the corre:- sponding hydrazone, the. resulting'compound has the formula More importantly in connection with the presentiinvention, the hydrazides-are used to produce reaction products with aldoses or ketoses. These sugars :give two types of compounds: normal bydrazones if the reaction'is carried out: using one mole of hydrazine to one mole of grape sugar, for example,

Ifhowever, an excessof the' hydrazone is1-used, anosazonetis-formed.

in which formulation COB represents again thebetaine' residue. An example of producing. the osazones insitu in a hydrocarbon distillate for example, is as follows:

100 parts by weight of hydrocarbon distillate containing 1% of betaine hydrazide. is warmed one water bath to about 90 with 1 part by weight of grape sugar and 2 parts of glacial acetic. acid, agitation being continuously carried on for about an hour. The osazone likethe hydrazone in the earlier example, is distributed between the two layers, both in. the hydrocarbon layer and in the Water layer, the mixture is allowed to settle, the hydrocarbon layer containing osazone is separated, washed with dilute alkali and then with water. This is an example of the production of an osazone in situ. in a hydrocarbon which may be of the gasoline range. for motor fuel or. 01"lubricating oil'range', while the osazone present'in' the water layer may be separated.

Particularly important for present purposes istthefact that the betaine hydrazide may be utilized to. formahydrazone or osazone with'the esterofa sugarwith a 'hetaine', thus having two-- betaihe residues lpresentzin the molecular aszre'piresente'd by the formula;

where COBxrepresents. thebetaine residue; and S represents the sugar residue. are particularly desirably; used in accordancezwith the present invention. as. antioxidants for: either. glyceri'de 0118 or. for thehydrocarbon: distillates.-.

The hydrazones and osazones'produced'fi'omi theesugars may: be esterified. with acidsbothtinorganic and. organic, monobasic: and -.polybasici; togive full or partial esters. Thus fatty acids, lower and higher as hereinabove set-forth-ior producing soaps, aromatic acids, etc., maybe used to modify the solubility of 1 these-compounds. Polybasic acidsif used such as phosphoric, sulphuric,"

phthaiic, polysulfonic, etc, to form partial esters' should have the remaining acidityneutralized as by" alkalis; alcohols, etc., or converted into metal; particularly'heavy metal derivatives.

The hydrazides may bereacted with beta diket-ones or beta ketone acid estersto form ringcompounds containing nitrogen for" example; pyr'azones and pyrazolones. Thus with. acetacetic estermetliyl pyrazolones' are formed the reaction w.th such ester and betaine hydrazidebeing exemplary;

The hydrazones, osazones, pyrazolesandpyrazolones may be looked upon as substitutedhydra zines in that. the osazones are compounds containing a reaction product of a hydrazine: group: Withboth a ketone andlanialdehyde.

Having thus set forthmy invention, Iclaim':

1'. A composition containing a' glycerid'e; and as an antioxidanttherefor, the reaction product? of'a betaine, a sugar'and an acid;.

2. A composition containing a glycerid'e' and;

as an antioxidant therefor, the reaction product of a betaine and a sugar;

3. A composition as set forth inclaim 1, in which the sugar 'i'sia monosaccharide;

4; A. composition as set forth in claim. Lin which the sugar is a hexose. Y

5'. A composition as. setf'orth in claim 1;, in which the acid is anzinorganicv acid;

,6.IA composition asset forth in claim 1, in which the acidlisan'organic acid.

7. Alcomposition. as set forth inclaim 1,.in which the acidis a fatty acid."

8. A. composition as s.et ..forth in. claim 21in which the sugar. .is a-monosaccharide.

9.. A.composition as. set forth .in claim 2;,in which the. sugar isa hexose.

10..A.composition. as set. forth inuclaim 4,.in whichmheacidis an inorganic. acid.

11. A composition as set forth in claim 4, in whichthe acid is an organic acid.

.12..A.compositionas set.f.orth in claim. 4, whichv thev acidis. a jattyacid...

13. A composition as set forth in claim..4 .i'n

which the acidincludes both inorganic and organic acids.

14. A-composition assetforthin claim 1 in which the betaine-v is lycine and the sugaris leulose, and the acid oleic acid.

15.- A- composition asset. forth in claiml inwhich the. betaineis .lycine,-. the sugar, is .leulose: and the-acidis laur'ic acid;

16.. A composition asset forth in. claim-Zinq which the betai-necis 'lycine; and the sugar dextrose;

SOL .SI-IAPP-IRIQ- Noreferences'cited';

Such complexes. 

1. A COMPOSITION CONTAINING A GLYCERIDE AND AN AN ANTIOXIDANT THEREFOR, THE REACTION PRODUCT OF A BETAINE, A SUGAR AND AN ACID. 